High-molecular compounds of the polyamide type and process of producing same



Patented Nov. 9, 1943 HIGH-MOLECULAR COMPOUNDS OF THE POLYAMIDE TYPE AND PROCESS OF PRO- DUCIN G SAME Hanns Uier, Ludwigshaten-on-the-Rhine, Germany; vested in the Allen Property Custodian No Drawing. Application August 25, 1939, Serial No. 291,931. In Germany September "I, 1938 2 Claims.

The present invention relates to high molecular compounds oi the type polyamides and a process of producing same.

In U. 8. application Ser. No. 252,630, filed on January 24, 1939, in the names of Hanns Uter, Willi Schmidt and Max Mattauch there has been described a process for the production of high molecular compounds similar to polyamides by reacting amines having at least two reactive amino groups separated from each other by at least two carbon atoms with unsaturated, in particular alpha-beta-unsaturated, monocarboxylic acid substances (i. e. the said acids themselves or their derivatives) at temperatures at which amide formation between at least two molecules of the amino acids formed from the reaction components takes place. 7

I have now found that high molecular compounds similar to polyamides can be obtained by heating monoarylamino carbonylic acid substances (i. e. the said acids themselves or their derivatives) obtainable by adding primary monoarylamines on unsaturated monocarboxylic acids, preferably M a-unsaturated monocarboxylic acids, or their derivatives, at temperatures at which amide formation between at least two molecules of the said amino carboxyllc acid substances takes place. Monoarylamino carboxylic acid substances of the said kind produced in any desired manner may be started with.

As suitable starting materials there may be mentioned for example phenyl-, tolyl-, xy1yl-, ethylphenyl-, butylphenyl-, chlorphenyi-, alkoxyphenyl, hydroxyalkyphenylfi-amino carboxylic acids,- for example the 3- amino propionic or butyrlc acids etc. substituted by the said substituents and also the corresponding compounds containing naphthyl instead of phenyl radicals. When the free acids are employed water is split 03 in the reaction; ii, however, esters of the said acids, for example methyl-, ethylor butylesters are employed the corresponding alcohols are split off. In the case of amides ammonia is split on.

The reaction consists probably in a formation of long chain polyamides according to the following scheme:

A preferable modification of carrying out the process consists in starting with unsaturated, preferably o-p-unsaturated, monocarboxylic acids or their derivatives and primary monoarylamines.

dodecylphenyb,

From these components the monoarylamlno carboxylic substances are first formed and these undergo the conversion according to the above scheme.

The conditions under which the conversion takes place are usually the same as described in the said application Ser. No. 252,630. By suit- Example 1 500 parts of phenyl-p-aminopropionic acid are heated under ordinary pressure for 20 hours at from 180 to 185 C. and then for 22 hours at 2'05 to 215 C. A yellowish resinous product is obtained which is not soluble in water, scarcely soluble in hydrochloric acid but soluble in hot ethyl alcohol.

Example 2 400 parts of phenyl-p-aminopropicnic acid are heated in a bath for 1% hours under ordinary pressure at from to (2., then for 21 hours under a pressure of 20 to 25 millimeters (mercury gauge) at 170 to 0., and finally for 23 hours under a pressure of 20 millimeters (mercury gauge) at to 200 C. A yellow resinous product is obtained which is not soluble in hot alcohol, butanol and methyl acetate and compatible with acetyl cellulose. An addition of the product to acetyl cellulose improves the adhesive power of coatings obtainable therewith.

Similar products are obtained if 1000 parts of a '72 per cent aqueous acrylic acid solution are slowly allowed to flow to 930 parts of aniline while stirring-and heating on the water-bath,

heating being continued for 4 hours at about N.OH1.CHs-C O OH -D 8 100 C. while stirring in order to evaporate the water and the temperature then being raised as indicated in the first paragraph oi this example. By varying the heating conditions, for example the duration of heating. the properties 01 the products, especially their solubility in organic solvents, may be influenced in a far-going degree.

From other aryl-p-amino carboxylic acids, such as mono-metatolyl-p-aminopropionic acid, a-naphthyl-p-aminopropicnic or butyric acid and the like, similar products may be obtained in analogous manner. Instead of the iree acids their esters, for example their methyl-, ethylor butylesters, or their amides may be employed.

What I claim is:

1. The process for producing high molecular compounds which comprises subjecting to a continued heat treatment a substance selected from the class consisting of acrylic acid and the amide forming derivatives thereof together with a pri mary monoarylamine at a temperature at which formation of long-chain polyamides takes place by interaction of a larger number 6'! molecules or the amino carboiwlic acid formed by adding the saidl amine on the double linkage of the acrylic ac 2. High molecular polyamides derived from a substance selected from the class consisting of acids corresponding to the formula RhNECHaCHaCOm.

wherein R1 represents an aryl radicle and the amide-forming derivatives of said acids by continued heat a treatment at a temperature at which formation of long-chain polyamides by interaction or a larger number of molecules of the said acids takespiace.

' HANNB UI 'ER. 

